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Periodicity of Single-Molecule Magnet Behaviour of Heterotetranuclear Lanthanide Complexes across the Lanthanide Series: A Compendium.

Accepted version
Peer-reviewed

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Authors

Izuogu, David Chukwuma  ORCID logo  https://orcid.org/0000-0002-1497-2308
Asegbeloyin, Jonnie N 
Zhang, Haitao 

Abstract

Acetato-bridged palladium-lanthanide tetranuclear heterometallic complexes of the form [Pd2 Ln2 (H2 O)2 (CH3 COO)10 ]⋅2 CH3 COOH [Ln2 =Ce2 (1), Pr2 (2), Nd2 (3), Sm2 (4), Tb2 (5), Dy2 (6), Dy0.2 Y1.8 (6''), Ho2 (7), Er2 (8), Er0.24 Y1.7 (8''), Tm2 (9), Yb2 (10), Y2 (11)] were synthesised and characterised by experimental and theoretical techniques. All complexes containing Kramers lanthanide ions [Ln3+ =Ce (1), Nd (3), Sm (4), Dy (6), DyY (6''), Er (8), ErY (8''), Yb (10)] showed field-induced slow magnetic relaxation, characteristic of single-molecule magnetism and purely of molecular origin. In contrast, all non-Kramers lanthanide ions [Ln3+ =Pr (2), Tb (5), Ho (7), Tm (9), Y3+ (11) is diamagnetic and non-lanthanide] did not show any slow magnetic relaxation. The variation in the electronic structure and accompanying consequences across the complexes representing all Kramers and non-Kramers lanthanide ions were investigated. The origin of the magnetic properties and the extent to which the axial donor-acceptor interaction involving the lanthanide ions and an electron-deficient d z 2 orbital of palladium affects the observed magnetic and electronic properties across the lanthanide series are presented. Unique consistent electronic and magnetic properties of isostructural complexes spanning the lanthanide series with properties dependent on whether the ions are Kramers or non-Kramers are reported.

Description

Keywords

electronic structure, heterometallic complexes, lanthanides, magnetic properties, palladium, single-molecule magnets

Journal Title

Chemistry

Conference Name

Journal ISSN

0947-6539
1521-3765

Volume Title

26

Publisher

Wiley

Rights

All rights reserved